Polyazo dyestuffs



United States Patent POLYAZO DYESTUFFS Hans-Rudolf Byland, Riehen, nearBasel, Switzerland, assiguor, by mesne assignments, to Saul & (10.,Newark, N. J., as nominee of Fidelity Union Trust Company, executivetrustee under Sandoz Trust N Drawing. Application October 7, 1955 SerialNo. 539,258

Claims priority, application Switzerland October 20, 1952 6 Claims. (Cl.260-168) wherein x represents OH, OCH;,, --OC H OCH .CO0H or COOH, with2 mols of an aminoazo compound of the general formula HO COOH HOaS- NH-RH0 (II) wherein R represents alkyl, hydroxyalkyl, alkoxyalkyl,cycloalkyl, aralkyl'or aryl, and the nucleus E may carry furthersubstituents commonly present in azo dyestuffs, or by coupling 1 mol ofthe first named component simultaneously or in either order with 1 molof an aminoazo compound of this type and 1 mol of a difierent:

aminoazo compound of the same general formula, or in either order with 1mol of an aminoazo compound of this type and 1 mol of any other azocomponent containing one or more groups capable of entering into complexcombination with metal:

The 4.4-diamino-1.1'-diphenyls of general Formula I which are suitablefor the preparation of the polyazo dyestuffs according to the presentinvention are 4.4-diamino-3 .3 '-dihydroxy-1.1'-diphenyl, 4.4-diamino-3.3'-dimethoxy-1.l-diphenyl, 4.4'-diamino-3.3-diethoxy-1.1-di phenyl,4.4-diamino-3 .3 '-dicarboXymethoxy-1.1-diphenyl and 4.4 diamino 1.1diphenyl 3.3 dicarboxylic acid. Preferred 4.4'-diamino-l.1-diphenyls are4.4'-diamino-3.3'-dimethoxy-l.l'-diphenyl and 4.4-diamino-1.1'-

diphenyl-3.3-dicarboxylic acid.

The aminoazo compounds of general Formula II are produced by couplingdiazotized Z-amino-l-hydroxybenzene-6-carboxylic acids in an acid mediumwith derivatives of Z-amino-S-hydroxynaphthalene-7-sulfonic acidsubstituted on the nitrogen atom. Suitable 2-amino-lhydroxybenzene-S-carboxylic acids are, for example, 2

amino 1 hydroxybenzene 6 carboxylic acid itself, 2 amino 1 hydroxy 6carboxybenzene 4 sulfonic acid, 2 amino 1 hydroxy 4methylsulfonyl-benzeno 6 carboxylic acid, 2 amino 1 hydroxy 6carboxybenzene-4-sulfonic acid amide and its derivatives methylated,ethylated, dimethylated and diethylated on the nitrogen atom of thesulfamide group, 2-aminoi hydroxy 6 carboxybenzene 4 sulfonicacidphenylamide, its compounds halogenated, alkylated, alkoxylated onthe nucleus of the phenylamide group, and

further derivatives substituted on the nucleus of the phenylamide groupsuch as the 2-amino-1-hydroxy-6-carboxybenzene 4 sulfonic acid (3carboxy 4 hydroxy)-phenylamide, also 2-amino-l-hydroxy-4-nitrobenzene 6carboxylic acid and 2 amino 1 hydroxy- 4 chlorobenzene 6 carboxylicacid. As substituents on the nitrogen atom of the2-amino-5-hydroxyphthalene- 7-sulfonic acid those primarily suitable arealkyl and cycloalkyl radicals, for example methyl, ethyl, propyl,hydroxyethyl and cyclohexyl, mononuclear aryl radicals such as phenyl,(2'- or 3- or 4-methyl)-phenyl, (3'- or 4' chloro) phenyl, (4 amino)phenyl, (4' carboxy) phenyl, (3 carboxy 4 hydroxy) phenyl, (3- or 4'sulfo) phenyl, (3'- or 4 methylsulfonyl)- phenyl, (3- or 4' sulfamido)phenyl, and also binuclear aryl radicals such as (4-amino)-'1',1".-diphenyl and aralkyl radicals such as benzyl. A preferredsubstituent on the nitrogen atom of the Z-amino-S-hydroxynaphthalene 7sulfonic acid is phenyl and substituted phenyl as defined above.

The new polyazo dyestuffs may be prepared with a symmetrical or anasymmetrical structure. For the production of asymmetrical products thetetrazotized 4.4-diamino-1.1-diphenyl of Formula I is coupled with e. g.two different aminoazo compounds of general Formula II.

It is also possible, however, to arrive at asymmetrical polyazodyestuffs by coupling 1 mol of tetrazotized 4.4- diamino-1.1'-diphenylof Formula I with 1 mol of an aminoazo compound of Formula II and 1 molof any other azo component containing one or more groups capable ofentering into complex combination with metal. Eminently suitable azocomponents of this type are for example 1hydroxybenzene-Z-carboxylicacid, l-hydroxy- 6 methylbenzene 2 carboxylic acid, 1 hydroxynaphthalene2 carboxylic acid, 2 hydroxynaphthalene 3 carboxylic acid, 1hydroxynaphthalene 4- sulfonic acid, 1 hydroxynaphthalene 4 sulfonicacid amide, 2 hydroxynaphthalene, 2 hydroxynaphthalene 4- or -6 or 7- or8 sulfonic acid, the corresponding sulfonic acid amides andmethylsultunes, 1- or 2 amino 5 hydroxynaphthalene 7- sulfonic acid, 1-or 2-phenylamino-5 hydroxynaphthalene- 7-sulfonic acid, Z-methylamineorZ-ethylamino-S-hydroxynaphthalene 7 sulfonic acid, 2-(4-hydroxy 3carboxy) phenylamino 5 hydroxynaphthalene 7- sulfonic acid, 2phenylamino 5 hydroxynaphthalene 7.4 disulfonic acid, 2 acetylaminoor 2-benzoylamino 5 hydroxynaphthalene 7 sulfonic acid, 2 aminoor 2benzoylamino 8 hydroxynaphthalene 6 sulfonic acid, 2 methylaminoor 2hydroxyethylamino 8 hydroxynaphthalene 6 sulfonic acid, 1 amino 8hydroxynaphthalene 4 sulfonic acid, '1 amino --8 hydroxynaphthalene 2.4disulfonic acid and l-aminoorZ-butyIamino-S-hydroxynaphthalene-3.6-disulfonic acid, also compoundswhich" couple in the adjacent position to an enolizable keto group, forexample S-pyrazolones, acyl acetic acid amides, acyl acetic acid arylamides, acyl acetic acid alkyl amides, malonic acid derivatives,barbituric acid derivatives, acetyl acetone, benzoyl acetone,4-hydroxy-l alkyl-quino lones and dihydroxyquinoline.

Examples of S-pyrazolones which which merit special coupling componentselected from those corresponding mention are 3-methyl-5-pyrazolone,1-phenyl-3-rnethyl-5- to the formula Z and those corresponding to anyother pyrazolone, 1-phenyl-3-methyl-5-pyrazolone-3'- or 4- compositionand containing one or more groups capable sulfonic acid amide, 1-(3- or4'-methylsulfonyl)-phenylof entering into complex combination withmetal. Pre- 3-methyl-5-pyrazolone, 1-(3'- or 4'-nitro)-phenyl-3- 5ferred significances of the symbol x are OCH and methyl 5 pyrazolone, 1(3' or 4 chloro) phenyl- --COOH, of the symbol R phenyl and substitutedphenyl 3-methyl-5-pyrazolone and 1-(2, 5-dichloro)-phenyl-3- radicals.methyl-S-pyrazolone. Particularly important, however, Aftertreatment ofthe dyeings with a polyalkylene polyare the acyl acetic acid arylamides, especially acetoacetylamine in the presence of a copper salt isparticularly aminobenzene and its derivatives substituted on thebenvaluable. zene atom by halogen atoms, amino, nitro, sulfonic acid.The invention is illustrated by the following examples; alkylsulfonyl,sulfonic acid amide, carboxylic acid and/ or the parts specified thereinare by weight and the temperaazo groups, alsol-acetoacetylaminonaphthalenes and 2- tures in degrees centigrade. Theproducts listed in the acetoacetylaminonaphthalenes which may be furthersubtable are equal in value to those described in the exstituted, the1-acetoacetylaminonaphthalene-monoand ditended examples; they areenumerated in tabular form sulfonic acids and theZ-acetoacetylaminonaphthalenesolely in order to save space. monoanddisulfonic acids. EXAMPLE 1 The coupling of 1 mol of the tetrazocompound of the 4.4-diamino-'l.l'-diphenyl of Formula I with 2 mols ofthe aminoazo compound of Formula II to give symmetrical dyestuffs isconducted simultaneously. When asymmetrical dyestuffs are to beproduced, the tetrazo compound of the 4.4'-diamino-1.l'-diphenyl ofFormula I may either be coupled first with 1 mol of an aminoazo compoundof Formula II and then with 1 mol of an aminoazo compound of Formula IIdifferent from the former, or it may be combined first with 1 mol of anaminoazo compound of Formula II and then With 1 mol of any other azocomponent, in which case the latter may also be coupled in the firstinstance. It is also possible to obtain valuable products by simultane-As Soon as tetrazo (iompouild entirely ous coupling of the tetrazocompound with a mixture of peared, the reaction mass is combined with asolution of two difierent aminoazo compounds of Formula II. The pains ofz'hydroxynaphthalene 4 parts of sodlum, first coupling reaction usuallytakes place fairly rapidly hy.drO.X1de and 300 Rafts of After hours andis carried out preferably in a sodium carbonate alkaagltatlop qm of thetnsazq dyesmfi ls line medium. The resulting intermediate compound isplated; It IS preclpltated mm the couplmgmass by means a of sodiumchloride and subsequently filtered off. The either isolated or usedfurther in solut on, without SPuCletl dyestufl is purified byredissolving and again precipi prepziratip In order to accelerate the56.6mm .coupling tated, filtered off and finally dried. It is a darkpowder reactlon It is of advantage to add an orgamc tamary base 40 whichdissolves in water with a dark blue colouration and 24.4 parts of4.4-diamino-3.3' dimethoxy-l.l-diphenyl 20 are tetrazotized in 150 partsof water and 150 parts of ice. To the tetrazo solution at 0-2 is addedan alkaline solution of 55.9 parts of the monoazo compound obtained byacid coupling of diazotized Z-amino-l-hydroxy-6-carboXy-benzene-4-sulfonic acid with Z-phenylamino-S- 25hydroxynaphthalene-7-sulfonic acid and 10 parts of sodium carbonate in1000 parts of water. Upon the addition of a solution of parts of sodiumcarbonate in 250 parts of water to the reaction mass, the one-sidedcoupling reaction is effected in a short time and the intermediatecompound so formed completely precipitated.

to reaction Solution, Pyridine quinoline or a dyes cotton and fibres ofregenerated cellulose in navy techmcal mlxture of Pyndme bases- The P Xblue shades. The dyeings possess very good tastness fufi thu formed areSalted 0171t from the $9111- to washing and perspiration and excellentfastness to n n f necessary, and are n filtered OE and dnedlight whentreated with copper sulfate in the course of a The dyestufis are readilysoluble in water and are appli- 45 one or two-bath process.

cable by the one-bath and aftercoppering'processes on The new trisazodyestutf corresponds to the formula 5 HO coon Hols -NH O H N=NQQN=N HHaC OH: H

cotton and fibres of regenerated cellulose in navy blue EXAMPLE 2 toblack shades of excellent fastness properties. They correspond to thegeneral formula 33.2 parts of 4.4 -d1am1no-3.3 -d1carboxymetl10xy-1.1'-diphenyl are tetrazotized'in 150 parts of Water and OOOH 150 partsof ice. To the tetrazo solution at 0-2 is given a solution of 31.5 partsof l-phenylamino-S-hy- N=N E droxynaphthalene-4-sulfonic acid and 10parts of sodium bicarbonate in 600 parts of water. Then 68 parts of H033solid sodium carbonate are strewn into the coupling mass in smallportions. After prolonged agitation the inter- I QQ 70 mediate compoundis completely formed and the tetrazo compound disappears. To thesuspension of the interz a; H mediate compound there is added a solutionof 55.9

Z (In) parts of the monoazo compound obtained by acid coupling ofdiazotized 2 amino 1- hydroxy-6-carboxybenwherein x, R and E have theabove-recited significances, zene-4-sulfonic acid with2-phenylamiho-S-hydroxynaphp and wherein the symbol Z stands for theradical of a thalene-7-sulfonic acid, 40 parts of sodium carbonate Theaftercoppered dyeings possess outstanding fastness and IOOparts ofpyridine in 1000 parts of water. After 7 solution of 17.7 parts ofacetoacetylaminobenzene in 200 several hours agitation at 0-2" theformation of the tris- P s Of Water is added to the tetraZO Solution;then 53 azo dyestulf is completed; it is precipitated from the parts ofsolid sodium bicarbonate are strewn into it in coupling mass by means ofsodium chloride and filtered small portions. After several hoursagitation at 02 oflf. The dyestufi is purified by redissolving, and isagain the formation of the intermediate compound is completed.precipitated, filtered off and finally dried. It is obtained To thesolution of the intermediate compound is added in the form of a darkpowder which dissolves in water an ice-cold solution of 55.9 parts ofthe monoazo comwith a blue colouration and dyes cotton and fibers ofpound obtained by acid coupling of diazotized Z-amino-lregeneratedcellulose in blue-grey shades. 011afterhydroxy-6-carboxybenzene-4-sulfonic acid with 2-phenyltreatmentwith copper sulfate, applied by a oneor two- 10amino-5-hydroxynaphthalene-7-sulfonic acid in 400 parts bath process,the dyeings become very fast to washing, of ammonia 200parts of pyridineand 600 parts of perspiration and light, 1 water. The trisazo dyestuffthus formed is completely The new trisazo dyestufi corresponds to theformula precipitated and is then filtered off It is purified by re- HOCOOH BOiH N|=N HO|S NH 01H N=N-QQN=N -HN H Hio- 1511, H H000 OOH EXAMPLE3 dissolving, and again precipitated, filtered off and finally dried.The dyestuif is a dark powder giving violet-red aqueous solutions, anddyes cotton and fibres of regenerated cellulose in violet-red shades. Onaftertreatment 24.4 parts of 4.4'-diamino-3.3dimethoxy-1.1'-diphenyl aretetrazotized in 150 parts of water and 150 parts of ice. The tetrazosolution in run into a solution of 111.8 parts of the monoazo compoundobtained by with copper Salts ill-a Q etwo-bath process, neutral acidcoupling of diazotized 2 amino l-hydroxy-o-cargrfiy Shades fast toWashlng, perspiration and llght are boxybenzene-4-sulfonic acid withZ-phenylamino-S-hytameddroxynaphthalene-7-sulfonic acid, 300 parts ofammonia The new trisazo dyestufi corresponds to the formula HO S NH 0,11

i l-on A OOH H 25% and 150 parts of water, in which solution also pyri-Further examples are noted in the following table. The dine is present.The tetrakisazo dyestuff thus formed is coupling reactions of the4.4'-diamino-1.1-diphenyl of, precipitated from the coupling mass bymeans of sogeneral formula I with the two azo components are cardiumchloride and then filtered Off. It is by reried out in accordance one ofthe operating rocedissolving, and again precipitated, filtered off andfinally dures described in Examples 1 to The fi t coupljlqlgv ,driei TheQ is a dark Powder which dissolves reaction is conducted preferably in asodium carbonate in water to give blue-coloured solutions and dyescotton U0 1 e bl h d and fibres of regenerated cenu 0s m navy He 8 a esd1t1on of, for example, pyridine, qumohne or a techmcal properties. Y

The new tetrakisazo dyestuff correponds to the formula trons areconducted simultaneously, it is of advantage H000 OH H0 0003 Gran N=N110th HNV 509E HOzS- NH om H 1150 ona H EXAMPLE 4 to add an organictertiary base to the coupling mass at 272 parts f 4 g m the start of theoperation, in order to accelerate the reacic acid are tetrazotized in250 parts of water. A neutral tion.

alkaline medium; the second may be effected with an ad-:

mixture of pyridine bases. When the two coupling reae-Z EXAMPLE 11000 onno 00011 N=N N=N H03 HN-- SOQH HOaS- NH 03H N=NC QN=N 11 Hi) 11 nEXAMPLE 8 no coon HO8S- NH our nois- N= WN=N H H5O on, no

EXAMPLE 31 Hogs HN-0 C-CN=N N:

on g 0 on Ha HO 0 EXAMPLE 39 parts of wetted-out cotton are entered into300 parts of water at 40. The bath is then prepared with a concentratedaqueous solution of 0.6 part of the dyestufi obtainable according toExample 1, and raised to the boil in minutes, during which time 3 partsof sodium sulfate in the form of a concentrated aqueous solution areadded in small portions. The dye liquor is maintained at the boil for afurther 30' minutes, then 1 part of sodium sulfate is added and the bathallowed to cool slowly to The material is rinsed well and treated for 30minutes in a fresh bath at containing 300 parts of water, 0.3 part ofacetic acid and 0.3 part of copper sulfate. The metallized dyeing thusobtained is rinsed and dried.

In place of the 0.3 part of copper sulfate in the aftertreating bath,0.3 part of a copper complex compound of the condensation product ofdiethylene triamine and dicyanodiamide (obtainable by the processdescribed in U. S. Patent No. 2,622,075) can be employed.

EXAMPLE 40 15 parts of the dyestuflf described in Example 1 are boiledwith parts of urea and 45 parts of triethanolamine in 360 parts ofwater. To the solution there are then added 400 parts of tragacanth 6%,20 parts of sodium phosphate, 40 parts of an anionic wetting agent apolyalkylene polyamine preparation containing copper salt, the print isrinsed again and dried.

What I claim is:

1. A polyazo dyestuff which corresponds to the formula HO COOH wherein xstands for a member selected from the group consisting of ---OH, OCH;,,OC H OCH .COOH and -COOH, y stands for a member selected from the groupconsisting of hydrogen, SO H, -SO .CH

and nitro, R stands fora member selected from the group consisting oflower alkyl, lower hydroxyalkyl, lower alkoxyalkyl, cycloalkyl, aralkyland mononuclear aryl radicals, and wherein Z is a radical of a couplingcomponent selected from the group consisting of a radical Z, of aradical of the hydroxynaphthalene series diiferent from Z and of aradical of the hydroxybenzene, pyrazolone, acetoacetylaminobenzene andacetoacetylarninonaphthalene series.

2,842,589 11 12 2. The polyazo dyestuff which corresponds to the formulaHO GOOH H O 35- NH 0 3H N=N N =N H H30 (3 C H; H

3. The polyazo dyestufl? which corresponds to the formula HOOC OH HOCOOH H038 EN 80311 HQsS NH 03H H Ha C O O C H: H

4. The polyazordyestufl which corresponds to the formula H000 OH H? COOHHO; HN-- SOsH H038 --NH 03H on H on HO 5. The polyazo dyestufi whichcorresponds to the formula H0 OOOH HOaS- ----NH 0211 OH moo 0m HO 6. Thepolyazo dyestuff which corresponds to the formula HO (F0011 HQ V 7 HOsS-NH N01 HN 0 G--EIJ-N=N-O;-C -N=N 0 0-011 L (30011 H 7 Ha H00 7 r IReferences Cited in the file of this patent UNITED STATES PATENTS2,507,754 Bossard et a1 May 16, 1950 2,638,468 Wehrli May 12, 19532,710,859 Kehrer et a1. June 14, 1955

1. A POLYAZO DYESTUFF WHICH CORRESPONDS TO THE FORMULA